in-situ groundwater monitoring · wavelength / nm 200 400 600 800 %t 0 50 100 150 200 dry co2 wet...
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1VALIDATE/ENSURE 99% STORAGE PERMANENCE
TEST AND VALIDATE THE USE OF CO2 MONITORING DEVICES
UNDER FIELD CONDITIONS
UNDERSTAND NATURAL BACKGROUND VARIABILITY
In-Situ Groundwater Monitoring
Migration into other Deep Formations
Migration into Shallow Aquifers LIBS
Continuous CO2Monitoring Devices
• Develop & demonstrate a suite of geochemically-based in-situ monitoring strategies for groundwater systems
• Determine sensitivities of techniques in real world conditions
FO Coatings
RISKS?
Fe
As LAB METHODS – COMPLEX WATERS
PA Karst Springs(Natural Analog)
Au-Nanoparticles
In-Situ Geochemical Monitoring
• Task 22: Direct CO2 Sensing in Groundwater
– deliver a inexpensive, continuous, downhole NDIR, telemetry-based sensing
method for the real-time detection of dissolved CO2 concentrations in
groundwater that are indicative of leaks from geological storage sites.
• Task 23: Distributed Fiber Optic Based CO2 Sensors for
Carbon Storage Applications
– deliver a viable CO2 sensing technology, that can monitor CO2 in geological
formations relevant for CCS applications. Demonstrate CO2 sensor with a
sensitive (< 1 percent) and selective/stable response in the presence of water
• Task 24: Laser Induced Breakdown Spectroscopy (LIBS)
– deliver a LIBS flow through apparatus capable of measurements of subsurface
fluids in contact with real and manmade materials under in situ conditions. This
work will deliver a laboratory based experimental apparatus that can withstand
elevated temperature and pressure which can be used alongside the field
deployable LIBS instrument that is currently being tested 2
Challenges to Current Practices
• Laboratory-based analyses can be time consuming, have
significant lag-time between sampling and analysis, and may
be impractical for real-time monitoring of leaks
• Even field deployments of existing sensing commercial
technologies require advances in packaging and methodology
• This work improves on the current practices:
– Advancing the science-base for potential novel in-situ analysis techniques
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• Non-Dispersive Infrared (NDIR)
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• Adapted from atmospheric sensors (Vaisala)
• < 1 mg/L lower limit
• NETL-adapted to sample pumped water
• Sensor modified for field deployment
• Commercial marine sensor being testedPI - Edenborn
Geochemical Monitoring: Direct Sensing: CO2 in Shallow GW
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Decatur IL ADM Plant, 2015-16
Brackenridge Field Site, Austin, TX 2016-2017
Central PA karst springs, 2017
Vaisala Sensor - Decatur Samples
Time of Equilibration (min)0 5 10 15
CO
2 (%
)
0
1
2
3
Time1000 1100 1200 1300 1400
CO
2, m
mol
/L
0
10
20
30
40 Well BFL01
10%
60%
100%
2017
CO
2, m
g/L
0
10
20
30
40
50
January February March
WEAVER
SPRINGHOUSE
SMULLTON
Geochemical Monitoring: Field Testing and Validation
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Nanomaterial Enabled Chemical Sensing
Nanomaterial Sensing Layer
▪ Engineered nanomaterials for chemical sensing parameters of interest
▪ Versatile and can be applied to any environmental parameters of interest
▪ Distributed interrogation permits “mapping” along the length of the fiber
▪ Examples: pH, CO2, and CH4
▪ Current project focuses directly on CO2
NETL RIC Optical Fiber Sensor Efforts are Targeted at Distributed Chemical
Sensing for Environmental Monitoring
Leverage In-House Capabilities in Functional Materials, Optical Sensing and Geochemistry
Products in 2018: 2 patents awarded, 2 peer-reviewed manuscripts publishedPI - Ohodnicki
Geochemical Monitoring: Nanomaterial Enabled Fiber Optic Chemical Sensors
Compatible with Distributed Interrogation
Geochemical Monitoring: Nanomaterial Enabled Fiber Optic Chemical Sensors
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An emphasis is being placed on metal-organic framework materials but recent efforts are also considering polymers as well.
CLIIT exp0
Evanescent Wave Absorption Based Sensors
Metal organic framework (MOF)
Polymers
Geochemical Monitoring: Nanomaterial Enabled Fiber Optic Chemical Sensors
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➢ MOF integrated wave-guide CO2 gas sensorDynamic response to various gases
Highly selective, sensitive films have been developed and demonstrated for CO2sensing in gas phase environments leveraging metal-organic framework materials.
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➢ MOF integrated wave-guide CO2 gas sensor
Geochemical Monitoring: Nanomaterial Enabled Fiber Optic Chemical Sensors
ACS Sensors, 2018, 3, 386-394.
Great promise for gas sensing of CO2.
Excellent selectivity to CO2.
Very fast (< 1 minute) response times
and excellent reversibility.
Improved scientific understanding of
sensing mechanism for the optical
fiber platform.
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➢ Rapid, selective and room temperature growth of MOF thin
films on conductive metal oxide for CO2 gas sensors
Geochemical Monitoring: Nanomaterial Enabled Fiber Optic Chemical Sensors
Cryst. Growth Des., 2018, 18, 2924-2931.
New growth techniques are being explored and developed for long-length fiber optic sensors compatible with distributed interrogation methods.
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Geochemical Monitoring: Nanomaterial Enabled Fiber Optic Chemical Sensors
➢ MOF integrated wave-guide CO2 gas sensor
➢ Water vapor impacts
Wavelength / nm200 400 600 800
%T
0
50
100
150
200Dry CO2
Wet CO2
Air permeable but water impermeable PTFE sleeve.
H2O N2, CO2
Without modifications to engineered sensing layers, water vapor has significant impacts on the response.
Water vapor impacts are being explored and techniques / learnings from field deployments underway for commercial technologies are being applied.
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Geochemical Monitoring: Nanomaterial Enabled Fiber Optic Chemical Sensors
➢ Test facility at the NETL “field testing” laboratory
The NDIR sensor being field tested can be applied “in-line” to prepare for future field testing efforts.
A new lab facility has been established to simulate groundwater with varying CO2.
➢ Surface modification of MOF
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Geochemical Monitoring: Nanomaterial Enabled Fiber Optic Chemical Sensors
2 Theta (deg.)5 10 15 20 25 30
XR
D in
tens
ity (a
.u.)
Pristine
MOF
Modified
MOF
Pristine MOF Modified MOF
Surface modifications to existing sensing layers are being explored to develop hydrophobic behavior, preliminary results show enhanced CO2 sensing with water vapor.
CO2 sensing results for a modified MOF in the presence of 80% relative humidity
Modification
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Geochemical Monitoring: Nanomaterial Enabled Fiber Optic Chemical Sensors
➢ Engineered hydrophobic polymers for CO2 sensing
PTFE sleeves help to mitigate water vapor cross-sensitivity and enable reversible sensing of CO2
Modifications to the engineered polymer based films are observed after water vapor exposure
Sensing materials that selectively absorb CO2 gas and mitigate water vapor are being developed
Geochemical Monitoring:
Laser Induced Breakdown Spectroscopy (LIBS)
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• Measurement of multicomponent system– Chloride Solutions of Ba, Ca, Mg, Mn, Sr
– Limits of Detection and Quantification vs. Pressure
– Emission decay vs. pressure vs. element
• Laboratory experiments successfully demonstrate that low-ppm range concentrations of Mg2+, Ca2+, Sr2+, Ba2+ and Mn2+ can be accurately measured in CO2-laden water at varied pressure conditions by using underwater LIBS.
Metal ions S R2 LOD(ppm)
LOQ(ppm) CO2
(bar)
Mg2+
0.0019 ± 2.93·10-5 0.9993 31.68 ±0.92
104.53 ±1.06 10
0.0023 ± 3.56·10-5 0.9996 31.12 ±0.78
102.71 ±2.54 200
0.0022 ± 1.87·10-5 0.9998 30.83 ±1.05
101.73 ±3.74 400
Ca2+
0.0114 ± 1.16·10-4 0.9996 2.48 ± 0.718.18 ± 0.20
10
0.0118 ± 3.85·10-4 0.9958 2.45 ± 0.628.09 ± 0.09
200
0.0111 ± 2.46·10-4 0.9980 2.67 ± 0.308.81 ± 1.01
400
Sr2+
0.0076 ± 6.83·10-5 0.99983.34 ± 0.11 11.02 ±
0.97 10
0.0080 ± 3.07·10-4 0.99563.04 ± 0.13 10.04 ±
1.34 200
0.0080 ± 1.37·10-4 0.99913.38 ± 0.31 11.15 ±
1.02 400
Ba2+
0.0037 ± 3.53·10-5 0.9997 4.38 ± 0.2114.42 ±
2.03 10
0.0038 ± 2.13·10-5 0.9998 4.86 ± 0.1216.05 ±
1.09 200
0.0036 ± 5.06·10-5 0.9994 3.91 ± 0.4512.91 ±
3.23 400
Mn2+
0.0050 ± 7.94·10-5 0.998910.47 ±
0.1334.53 ±
1.05 10
0.0062 ± 1.76·10-4 0.99687.42 ± 0.09 24.50 ±
1.00 200
0.0064 ± 1.06·10-4 0.99895.24 ± 0.05 17.27 ±
0.55 400
Goueguel, C.L. et al “Quantitative determination of metal ions in high-pressure CO2-water solutions by underwater laser-induced breakdown spectroscopy” in prep PI - McIntyre
Geochemical Monitoring:
Laser Induced Breakdown Spectroscopy (LIBS)
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Figure 5: Basic design of the monolithic PQSW Nd:YAG Pill laser. The high reflector is coated directly onto the Nd2+ doped YAG and the output coupler is coated onto the Cr4+ doped YAG. The two YAG crystals are bonded.
• Method and Device or Remotely Monitoring An Area Using
a low Peak Power Optical Pump, US Patent 8786840 B1
– Fiber delivers pump pulse and returns spectral signature– Laser can be designed to perform either LIBS or RAMAN excitation– Laser is 16mm long– Entire optical setup can be sealed to withstand pressure and temperature– Laser operation is dictated by selection of optical element parameters and
tailoring of input pump pulse
Miniaturized Probe Development
Geochemical Monitoring:
Laser Induced Breakdown Spectroscopy (LIBS)
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Figure 1: Layout of LIBS sensor head. Pump coupling lenses L1 = 25 mm and L2 = 50 mm, Beam expander L3 = -25 mm and L4 = 75 mm, Aspheric focusing lens L5 = 10 mm, Emission coupling lenses L5 and L6 = 50 mm. DCM = dichroic mirror, M = aluminum mirror, BP = 1064 nm bandpass filter, PD = photodiode.
.
• Initial prototype constructed around a 30mm optical cage system• Full operation validated with solids, liquids, and in air
• Geometry would allow access to 8in pipe• Second smaller prototype constructed around 16mm optical cage system
• Geometry would allow access to 4in pipe• Challenges with spark production and data quality
Miniaturized Probe Construction
Geochemical Monitoring:
Laser Induced Breakdown Spectroscopy (LIBS)
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• Modification of pumping light to activate the laser• Increased size of pumped volume inside the active material• Improvement of output beam quality (M2~1.04)
• Modification of output beam size with beam expander• Initial long spark production shielded light used for analysis• Initial long spark was inconsistent due to extended intensity distribution
• New compact spark due to improved intensity distribution• Reduced light shielding and more light available for analysis• Perfect consistency in location and time• Improved SNR and lower LOD
Challenges Overcome
Geochemical Monitoring:
Laser Induced Breakdown Spectroscopy (LIBS)
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Table 1: LODs for Ca, Sr, and K.
Element Line (nm)
LODA (ppm)
LOD (literature) (ppm)
Calcium 422.7 0.10 0.94B,† 0.047C 0.13F
393.4* 0.6F
Strontium 460.7 0.04 2.89B,†
421.5* 0.34D,# 407.8* 0.025G
Potassium 766.6 0.009 0.03B,† 1.2E 769.9 0.069
A – This study, B – Goueguel et. al. 2015 [21], C – Pearman et. al. 2003 [22], D – Fichet et. al. 2006 [23], E – Cremers et. al. 1984 [20], F –Knoop et. al. 1996 [24], G – Popov et. al. 2016 [25], * - Lines showed self-absorption over the concentration ranges used in this study, † - NaCl solution matrix, # - LIP on liquid surface
• Calcium, Strontium, Potassium measurement in solution• LOD in ppb range (below)
• Europium and Ytterbium measurement in solution• LOD 1-2 ppm range
• Europium and Ytterbium measurement in solid form• LOD 10-40 ppm (dependent on emission line used)
Data Collection and Validation
Accomplishments to Date
– Field deployment of commercial sensors is clarifying the baseline
information and methodologies for new tools under development
– Selective and sensitive CO2 sensing layers have been developed and
demonstrated based on metal-organic frameworks
– Efforts towards field deployment have been initiated including (1)
optimizing sensor layers for aqueous applications, (2) packaging and
testing under application relevant conditions
– Sensing layer modifications to improve hydrophobicity have
improved CO2 sensing performance, more work on-going
– Initial LIBS probe design tested and validated, and data acquisition
has been performed to demonstrate performance
– Weatherproof probe underway and flow through lab is in permitting
– 2 patents pending (LIBS), and 2 patents awarded with several other
in preparation (Fiber optic)20
Lessons Learned & Synergy Opportunities
– Opportunities exist to leverage on-going work in wellbore chemical
sensing under SuBTER research efforts within NETL R&IC
– Other geochemistry efforts in the Carbon Storage program can
provide insights to application relevant levels / performance metrics
– Optical fiber sensor efforts by other teams on physical parameter
monitoring can be used to aid and accelerate field deployments21
– Sensing layer stability and response in high water vapor conditions
requires additional sensing layer development
– Manipulation of LIBS laser pumping geometry and output to
improve performance and consistency
Lessons Learned
Synergy Opportunities
Synergy Opportunities
• Continued field-based collaboration to test new geochemical
monitoring techniques and tools under different CO2 storage
conditions (e.g. FO coated sensors)
• Natural analogs
• Controlled release sites
• EOR field systems
22NETL researcher, Hank Edenborn (NETL) at the Brackenridge Field Site (Austin, TX)
Project Summary
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• Geochemical monitoring methods/tools are being field
validated & baseline signals interpreted
• Information gained from knowledge of CO2 storage
systems is being used to inform development of novel
in-situ chemical sensing tools
• NDIR for CO2 in shallow systems: natural analog
successfully tested, CCS site deployment underway
• LIBS – lab validated, moving towards field prototype
• MOF coated FO sensor for direct chemical sensing - lab
validation in progress, field testing in upcoming 2 yrs
Appendix
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Benefit to the Program • Program Goals:
– Validate/ensure 99% storage permanence.
– Develop best practice manuals for monitoring,
verification, accounting, and assessment; site screening,
selection and initial characterization…
• Project benefits:
– There is a need to be able to quantify leakage of CO2 to the near surface
and identify potential groundwater impacts. This project works to develop
a suite of complementary monitoring techniques to identify leakage of CO2
or brine to USDW’s and to quantify impact.
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Organization Chart
NETL (PI)
Dustin McIntyre
AECOM
Dan Hartzler
Applied Spectra
Jong Yoo
Chunyi Liu
NETL (PI)
Paul Ohodnicki
AECOM
Ki-Joong Kim
NETL (PI)
Hank Edenborn
NETL
Task Technical Coordinator
Christina Lopano
NETL
Technical Portfolio Lead
Angela Goodman
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Task 22 Direct CO2 Sensor Schedule
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Task 23 Fiber Optic Sensor Schedule
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Task 24 LIBS flow Schedule
30
TCF Schedule
100%100%
50%
0%0%
Bibliography• P. R. Ohodnicki, C. Wang, T. D. Brown, and B. Kutchko, “METHOD OF EVALUATING PH USING A METALLIC
NANOPARTICLE INCORPORATED NANOCOMPOSITE-BASED OPTICAL PH SENSOR”, Filed March 2015,
S-11213.
• A. X. Wang, C-H Chang, X. Chong, K-J Kim, P. Ohodnicki, “SENSOR DEVICES COMPRISING A METAL-
ORGANIC FRAMEWORK MATERIAL AND METHODS OF MAKING AND USING THE SAME,” U.S. Patent,
No. US15019811.
• K.-J. Kim, P. Lu, J. T. Culp, P. R. Ohodnicki, “Metal−Organic Framework Thin Film Coated Optical Fiber Sensors: A
Novel Waveguide-Based Chemical Sensing Platform”, ACS Sensors, 2018, 3, 386-394.
• Hartzler, D.A., Jain, J.C., and McIntyre D.L., 2018. Development of a subsurface LIBS sensor for in situ groundwater
quality monitoring with applications in carbon sequestration, Scientific Reports (Submitted for Review)
• Jain, J.C., McIntyre, D.L., Goueguel, C.L., and Bhatt, C.R., 2017. LIBS sensor for sub-surface CO2 leak detection in
carbon sequestration. Sensors & Transducers, 214, 21-27.
• Hartzler, D.A., Jain, J.C., McIntyre, D.L., 2018. Development of downhole LIBS prototype for CO2 leak detection in
geologic carbon storage, SCIX Conference, Atlanta, GA
• Hartzler, D.A., Jain, J.C., McIntyre, D.L., 2018. Prototype LIBS sensor for sub-surface water quality monitoring, AIChE
Conference, Pittsburgh, PA
• Jain, J.C., McIntyre, D.L., 2017. Development of laser induced breakdown spectroscopy sensor to assess groundwater
quality impacts resulting from subsurface activities. IPEC conference, San Antonio, TX
• McIntyre, D.L., Woodruff, S.D., “Laser induced breakdown spectroscopy (LIBS) probe form simplified light collection
and laser operation,” US Non-provisional patent application No. 15794345 filed 10/26/2017.
• McIntyre, D.L., Woodruff, S.D., “Composite laser for producing multiple temporal ignition pulses,” US Non-provisional
patent application No. 16/011,846 filed 6/19/2018. 31